Preparation and production of catalysts.



JAMES DEWAB, OF LONDON, AND ADOLF LIEBMANN, OF WEYBHIDGE, ENGLAND,ASSIGNORS TO THE PROCTER AND GAMBLE COMPANY, OF CINCINNATI, OHIO, A

CORPORATION OF OHIO.

PREPARATION AN D PRODUCTION OF CATALYSTS.

Ho Drawing.

To all whom it may concern:

Be it known that we, Sir JAMns DEWAR, of 21 Albemarle street, London,England, and ADoLF LIEBMANN, of The Whim, Weybridge, in the countyk ofSurrey, England, both subjects of the ing of Great Britain, haveinvented new and useful Improvements in the Preparation and Productlonof Catalysts, of which the following is a specification.

It is well known that metallic catal sts can be produced by thereduction of t e1r oxids or hydrates by means of hydrogen.

Moissan first discovered the property of nickel, cobalt, and iron to becapable of producing catalytic action andhas. already pointed out thatthe most efficient action is obtained by the metal prepared by reductionof the hydroxid with hydrogen at the lowest possible temperature.

Later on Sabatier and Senderens found in their classic researches onhydrogenation that unsaturated compounds could be transformed in theaseous state into saturated compounds by t e action of hydrogen in theresence of the above named catalysts which had to be used in a veryfinely divided condition and the further found that copper was alsocapab e of acting as a catalyst.

The reduction of each of the oxids or hydrates of the before namedmetals by hydrogen commences at a definite temperature varying with eachof the oxids or hydrates.

We have found that the temperature at which the reduction by hydrogen ofsuch oxids or hydrates commences can be considerably reduced and this isof importance as the production of catalysts at a low temperature isvery advantageous, for various reasons. The lower temperature preventsthe possibility of the new molecular aggregations of the finely dividedmetals. It further renders it possible to produce the catalyst andefi'ect hydrogenation in one operation in the process of thehydrogenation of unsaturated oils and fats, at such a low temperature asto prevent decomposition of such oils and fats and one at which the Irapidity of the action is very great. This forms the subject matter ofour application of even date, Serial No. 842,538.-

Our present'invention consists in the re- I Specification of LettemPatent.

duction by hydrogen at a relatively low temperature of a mlxture of theoxids (either hydrated or anhydrous) of two or more of the catalyticmetals above referred to or of a mixture of the oxids of one or 'more ofthe said catalytic metals with palladium, platinum or silver in a finestate of division. A mixture of the oxids of one or more of the PatentedJune a, rare. I Application filed June 2, 1914. Serial No. 842,537. i

said catalytic metals along with silver oxid can also be employed.

In addition to the hydrated oxids and anhydrous oxids we find alsocarbonates suitable for the purpose of reduction. The mixture ofhydrates or carbonates to be used may be advantageously produced byprecipitation of a solution containing two or more salts in proportionswhich may be widely varied from simple molecular proportions. We do notlimit ourselves to an one method of preparing the mixture 0 thesecompounds. The mixture of anhydrous oxids may be obtained from thehydrates or nitrates or carbonates by heating. In practice'we find thatin preparing the anhydrous oxids from a mixture of nitrates, the use ofa mixed aqueous solution gives on evaporation a product which afterheating is particularly suitable for the reduction.

It is well known that a single catalyst like nickel can be formed on asupport such as according to a compound as defined in A with silveroxid.

D. The catalysts of the types A, B, and C produced on the surface ofporous substances.

The following examples will serve to'illustrate further how theinvention can be carried into effect but the invention is not conlid mil

Example I A solution prepared by dissolving 98.2 parts of nickel nitrate(containing 6 molecules of water of crystallization) and 9.3 parts ofcopper nitrate (containing 6 molecules of Water of crystallization) isheated and precipitated while hot with a slight excess of caustic soda.The mixture is then boiled and the precipitate collected on a filter andwashed with hot water until free from soluble salts. It is subsequentlydried on the water bath and the drying is finally completed in an ovenat a temperature of about 130 centigrade. The reduction by hydrogen ofthe oxygen compounds thus obtained is nearly completed after about 2hours at about 170 centigrade.

Ema/mple II.

A solution prepared by dissolving 44.6 parts of cobalt nltrate(crystals) parts of copper nitrate (crystals is heated and precipitatedwith a slight excess of caustic soda. The mixture is then boiled and theprecipitate collected on a filter and washed with hot water until freefrom soluble compounds, then dried on the water bath. The reduction byhydrogen of the oxygen compound thus produced is practically completeafter four hours at about 180 centigrade. The reduction product contains10 per cent. of copper and 90 per cent. of cobalt.

Ewa/mple III.

A solution prepared by dissolving parts of iron nitrate (crystals) and4.65 parts of copper nitrate (crystals) is heated and precipitated whilehot With slight excess of caustic soda. The mixture is then boiled,filtered and washed until free from soluble compounds, then subsequentlydried on the water bath. The reduction by hydrogen of the oxygencompound thus obtained is practically complete after 2% hours at fromabout 275 to 320 centigrade. The reduction product contains 10 percent.of copper and 90 per cent. of iron.

v Emample IV.

A solutionof .218 parts of'platinum chlorid and 49.1 parts of nickelnitrate (crystals) ,is poured into a boiling aqueous solution containingthirty parts of caustic soda and vtwo parts by weight of 40 per cent.formalin. The boiling is continued for some time and the precipitateseparated is collected on a filter, washed until free from soluble saltsanddried on the water bath. On being reduced with hydrogen the reductionis practically complete after four hours at about 200 centigrade and thereduction and 4.65

product contains 1 per cent. of platinum and I 99 per cent. nickel.Mixtures of nickel hydrate and palladium can be prepared in the mannerabove described with a practically similar result.

E trample V.

Ewample VI.

42 parts of kieselguhr are impregnated with 100 parts of a solutioncontaining 121} parts of nickel nitrate (crystals) and 1% parts ofcopper nitrate (crystals). A solution of 11 parts of sodium carbonate in100 parts of water is added and the whole well stirred together. Therecipitate is collected on a filter, washed t oroughly until free fromsoluble salts and dried on the water bath. The reduction of the oxygencom pound thus obtained is practically complete after one hourstreatment with hydrogen at about 170 centigrade, and the metal-bearingportion of the product contains after treatment for another hour atabout 180 centigrade 99 er cent. of metallic contents.

For simplicity and convenience, we designate the metals of group Aabove, viz., nickel, cobalt, copper and iron, as"heavy metal catalysts;and the metals of group B, viz., palladium, platinum and silver, asnoble metal catalysts. It will be observed that the inventioncontemplates the preparation of mixed catalysts consisting either of aplurality of the heavy metal catalysts, or of one or more of these heavymetal catalysts in association with a noble metal catalyst. Whatever itscomponents may be, the mixed catalyst may be used by itself, or appliedto a orous support. The term metal of the nic el group is used toinclude nickel, cobalt and iron.

What we claim is 1. For use in the hydrogenation of fats and, oils, amixed catalyst containing a plurality of heavy metal catalysts and anoble metal catalyst.

2. For use in the hydrogenation of fats and oils, a mixed catalystcontaining. a plurality of heavy metal catalysts.

3. For use in the hydrogenation of fats and oils, a mixed catalystcontaining nickel and copper.

4. The hereindescribed method of preparsufficiently low temperature inga mixed catalyst, which consists in subjeeting a, mixture of compoundsof catalytic metals, one at least of which is a heavy metal catalyst, toreduction by hydrogen at a to avoid producing new molecular aggregatesof the finely-divided metals.

5. The hereindescribed method of preparing a mixed catalyst, whichconsists in subjecting a mixture of compounds of catalytic metals, oneat least of which is a heavy metal catalyst, to reduction by hydrogenata temperature approximating 200 C.

6. The hereindescribed method of preparinga mixed catalyst, whichconsists in subjectlng a mixture of compounds of catalytic metals, oneof which belongs to the nickel group, to reduction by hydrogen, at asufficiently low temperature to avoid producing 2 new molecularaggregates of the finely-divided metals.

7. The hereindescribed method of prepar tit ing a mixed catalyst, whichconsists in subjecting a mixture of compounds of catalytic metals, oneof which is nickel, to reduction by hydrogen, at a sufliciently lowtemperature to avoid producing new molecular aggregates of thefinely-divided metals.

' 8. The hereindescribed method of preparing a mixed catalyst, whichconsists in subjecting a mixture of compounds of nickel and copper toreduction by hydrogen at a sufficiently low temperature to avoidproducing new molecular aggregates of the finely-divided metals.

In testimony whereof We have signed our names to this specification inthe presence of two subscribing witnesses.

JAMES DEWAR. ADOLF LIEBMANN.

Witnesses:

HERBERT D. JAMnsoN, GILBERT B. BYRON.

